Azoic dyestuffs of the benzotriazole series



Patented Apr. 13, 954

AZOIO DYES TUFFS OF THE BENZO- TRIAZOLE SERIES .Mario Scalera, Somerville, and Frederic Henry Adams, Bound Brook, N. J assignors to American Cyanamid Company, New York, N. Y., a

corporation of Maine No Drawing. Application September 27, 1951, Serial No. 248,655

9 Claims. (01. 260-157) r This invention relates to a new series of azo coloring matters having the following formula:

N it on \N H N=NA13 in which R is a carbocyclic aromatic radicaL'the CONHR group being ortho to the hydroxy group and Ar is the radical of a diazotizable amine.

The dyestuffs of the present invention show a wide variety of attractive shades, particularly browns and tans. It is an advantage of the present invention that they are prepared by the ordinary process of coupling diazotized amines with arylides having the. formula CONHR In general, any of the ordinary diazotized amines may be used. A few typical amines include ani.-.

line, .toluidines, anisidines and phenetidines, sulfanilic acid, naphthionic acid, 4-chloro-2-methylaniline, alphaand beta-naphthylamine, 1- naphthylamine 6 sulfonic acid 1 naphthylamine-4,8-disulfom'c acid, benzidine, dianisidine, -ch1oro-2-methoxyaniline, 2-chloro 5 aminotoluene-4-sulfonic acid and the like. The coupling reactions proceed smoothly and require no Example 1 coon N--- on .t \N H A nickel lined, steel autoclave is charged with an intimate mixture of 20 parts of S-hydroxy- 1,2,3-benzotriazole, 95.5 parts of anhydrous potassium carbonate, and parts of solid glass beads. The mixture is heated in the autoclave with open vent for 6 hours at 150-165" C., and then under 600 lbs. of carbon dioxide for 16 hours at ISO-190. The contents of the autoclave are then dissolved in 600 parts of water, decanted from the glass beads, heated at 50"With 5 parts of charcoal and 5 parts of siliceous filter aid, and filtered. The product separates onlacidification.

It can be purified by solution in sodium hydroxide followed by acidification to pH 6, filtration, and charcoal decolorization. Onstrong acidification the product separates and may be filtered and recrystallized from water. It melts at approximately 210 C. It couples with dliazotized pnitraniline in acid solution to give a bright reddish-orange product, and in alkaline solution to give a reddish-violet product.

Example? comical,

5-hydroxy-1,2,3-benzotrlazolei-carboxy-lic anilide A solution of 2.55 parts ofthe above prepared 5-hydroxy-1,2,3-benzotriazole-4-carboxylic acid in 110 parts of chlorobenzene is dried by'distilling out 5 parts of solvent,'treated with 1.89 parts of aniline, and cooled to 70 C. There is then gradually added at this temperature a solution of 0.85 part of phosphorus trichloride in 50 partsof chlorobenzene. The mixture is heated to C., andthe reaction completedby refluxing until evolution of hydrogen chloride ceases. The resulting solution is cooled to room temperature, filtered, and extracted with aqueous sodium hydroxide. The product separates on acidification and is filtered. If desired, it can be crystallized from alcohol, and melts at approximately 188 C.

This arylide couples in alkaline solutions with diazotized p-nitroaniline to give a dark reddishbrown dye, soluble in caustic alkali and reprecipitated by acetic. acid. Diazoti zed 2,5-di'chloroaniline gives analkali soluble brownish-orange dye;

Example 3 O C H:

B-hydroxy-1,2,3-benzotriazole-4-carboxylic-o-anisidide This compound is prepared in excellent yield from o-anisidine by the procedure described above for the anilide. It may be crystallized from alco- 11-01. The pure material melts .at approximately 15 213 C.

Example 4 Example .5

5-hydroxy-1,2,3-benzotriazole-4-cazhoxylic alphanaphthylaln'ide Prepared by the above described procedure, and crystallized from alcohol, this product melts at approximately 214 (3.

simple 6 f5-hydrox y-1,2, 3-benzotriazole-4carboxylic benzidide This product is prepared by the above described procedures. It shows no melting point up to 300 C.

Emample 7 -meidosalicr ic acm' A solution of 16 parts of i-aminosalicylic acid in 50 parts of water and 24 parts of 5 N sodium hydroxide solution is treated with 8.1 parts of potassium cyanate, and stirred until solution is complete. The resulting solution is cooled to 1015 C., and carefully acidified with 5 N hydrochloric acid. The resulting thick white precipitateis heated to boiling to .redissolvatreated with charcoal, filtered, cooled, and :further acidified by additional hydrochloric acid. The product is filtered, and may be recrystallized from water. It melts at approximately 209 0.

Example 8 NH1C.ONH 0H 5-(mtolylazo)-d-ureidosalicylic acid A solution of 38.6 parts of p-toluidine in 234 parts of .5 N hydrochloric acid and 500 parts of Water is diazotized in the normal way at 2-3 C. with 5 N sodium nitrit solution. The resulting diazo solution is added with stirringto a solution of 84.5 parts of the above prepared :4'-ureido'- salicylic acid in 800 ml. of water and 260 parts of 5 N sodium hydroxide, additional sodium hydroxide being added as necessary to maintain strong alkalinity. The reaction mixture is diluted with 500 parts of water, acidified to D 3 th hydrochloric acid after completion of the couplinghand.

filtered. The brown dye obtained dried at 50 'C.

Example!) 5-amino-4-ureidosalicylic acid To 1000 parts of water and 118 parts of 5 N sodium hydroxide at 60 0., there is added 44.3 parts of the above prepared 5-(p-tolylazo)-4- ureidosalicylic acid and 50 parts of sodium hydrosulfite. The mixture is heated to until practically-colorless, held at this temperatureapproxs i imately one-half hour longer, filteredhot, cooled to 30"., and washed with toluene. Removal of the p toluidine iscompleted by adding to thezaqu'eous solution '24 parts -.of 5 'Nlsodium hydroxide solu-i t-ion, and repeating the toluene extraction; The washed solution is then .cooled to 5 C. and acidifled to precipitate the white product. The yield can be increased somewhat by salting. The product melts with decomposition in the range 235-240 C., charring at lower temperatures.

Example 10 Ifil .011 N '5-hydroxy-IL,2,3-11enzotriazole-dcarboxylicacid i A solution 40f 4.2 parts of the above prepared S-am'ino-4-ureido-sa1icylic acid in parts of water and 30 parts of 5 N sodium hydroxide is treated with 16 parts of. .5 .Nhgydrochloric acid to precipitate the starting material in finely divided form. The resulting slurry is cooled to 10 C. and treated with approximately parts of 0.1 N sodium nitrite solution, which is added as fast as it reacts. When the reaction is complete, as evidenced by a permanent excess of nitrite, the preeipitateis .iilteredand .driedi; I; desired, it

5. may be purified by boiling with an equal weight of decolorizing charcoal in 100 times itsweight in water, filtering,and acidifying with dilutehydrochloric acid. This material does not melt but 6 tized 3-nitro-4-aminoanisole"in 10,000 parts of water. The resulting dyeing is reddish brown. The second skein is dyed an orange-brown shade in a similar way from the zinc chloride stabilized gradually decomposes at temperatures in the 5, diazo of 2,5-dichloroaniline. range of 280 C. It couples with diazotized p- The following table gives the shades of other nitraniline in acid solution to give a yellowishdyeings made by the sametechnique:

Coupling Component Diazo Component Shade 1. dihydrloiybenzotriazole-i'carbox- 3-nitro-4-aminoanisole-.. R-eddish tan. CMIIIBI'. 2. EfiIYdIIiFYbQHZOtlifiZOle--cdrbOX- 2,5-dich1oroaniline. Yellowish tan.

cam: e. '3. -hydroxybenzotriazoleq-carbox- 3-nitro4 amlnoauisoleu. Reddish tan.

ylic alphanaphthylamide. 4. 5-hydroxybenz0triaz0le-4-carbox- 2, 5-dichloraniline Ycllowish tan.

yllc alphanaphthylamide. 5. 5]- hy;)dro1 llzienzotriazole-d-earbox- 3-nitro-4-aminoanlsole Orange-brown. ylC enz e. l 6., 5-hydroxybenzotriazole-4-carbox- 2,5-dichloroaniline Orange-tan.

ylic benzidide. 7. 5-hydroxybenzotriazolei-carboxy 3-nitro-4-aminoanisole-. Reddish brown.

o-anlsldidc. 8. 5-hydroxybenzotriazole-i-carboxy 2,5-dichloroaniline Yellowish brown.

o-anisidide.

orange product, and in alkaline solution to give a We claim: deep bluish-violet product. 1. An azo dyestufi of the formula:

Example 11 CONHR N--- CH N- OH ILL Q N=NAr CQNHCaHs N \g H 5-hydroxy-1,2,3-benzottlazoleG-catboxylic anilide The procedure described above is followed, using 490 parts of dry chlorobenzene, 13.5 parts of aniline, and 17.9 parts of 5-hydroxy-1,2,3-benzotriazole-fi-carboxylic acid. An excellent yield of product is obtained. It may be purified by dissolving in hot dilute caustic, treating with decolorizing charcoal, filtering, and acidifying. It decomposes at approximately 253 C.

Example 12 NHC g/ C 0 0H5 p-Chloroaniline (10.4 parts) is diazotized in the ordinary way with hydrochloric acid and sodium nitrite and added with stirring to a solution of 21.6 parts of the above prepared 5-hydroxy-1,2,3- benzotriazole-fi-carboxyanilide in 1600 parts of water, 80 parts by volume of molar sodium carbonate solution, and 160 parts by volume of molar sodium carbonate solution. Additional sodium carbonate is added as necessary to maintain alkalinity to phenolphthalein. When coupling is complete, the resulting deep brown solution is acidified, and the brown dyestufl' filtered, washed, and dried at 100.

Example 13 A solution is prepared from 50 parts of the above prepared 5-hydroxy-1,2,3-benzotriazole-6- carboxylic anilide, 200 parts of alcohol, 350 parts of 5 N caustic soda, and 9500 parts of water. The resulting solution is used to pad 500 parts of cotton yarn, which is then wrung out and divided into 2 equal parts. One of the resulting skeins is developed by immersion in a bath containing 100 parts of the zinc chloride double salt of diazoin which R and Ar are carbocyclic aromatic radicals.

2. An azo dyestuff of the formula:

C ONHR ILNlv- OH \N N=NAT in which R and Ar are carbocyclic aromatic radicals.

3. An azo dyestufi of the formula:

in which Ar is a carbocyclic aromatic radical.

4. An azo dyestuff of the formula:

0 O-NHOGNH-G o 5. An azo dyestuff according to claim 2 in which R and Ar belong to the benzene series.

6. An azo dyestufi of the formula:

OHIO

(IJONH on rawO-ol I 2,895,896 7 8 7. Anazioflyesmfimathemmma: K1111 1120 dyestiifi according to iclaim 7 in which both Arand R aremononuoleazr.

\9. Anazo dyestufi-nfthe farm-111a:

in which R and :are carbocyclic aroma-tic radicals. 10

References Cited .in the file 01 this patent STATES PATENTS Number Name Date 2,308,023 Peterson Jan. 12, 1943 2,346,531 Allen et a1 Apr. 11, 1944 2,448,870 Dickey'et a1. Sept. 7, 1948 Vii.-- 

1. AN AZO DYESTUFF OF THE FORMULA: 